WO2000005192A2 - Alkyl allyl amines and low voc hair styling compositions using same - Google Patents
Alkyl allyl amines and low voc hair styling compositions using same Download PDFInfo
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- WO2000005192A2 WO2000005192A2 PCT/US1999/016301 US9916301W WO0005192A2 WO 2000005192 A2 WO2000005192 A2 WO 2000005192A2 US 9916301 W US9916301 W US 9916301W WO 0005192 A2 WO0005192 A2 WO 0005192A2
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- alkyl
- group
- hair
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- 0 CC*1C(C)(C)CN(C)CC(*)(*CC(C)(CC)CC)*C1 Chemical compound CC*1C(C)(C)CN(C)CC(*)(*CC(C)(CC)CC)*C1 0.000 description 3
- VQMPTVQCADWACQ-UHFFFAOYSA-N CCC(C)(CC)N Chemical compound CCC(C)(CC)N VQMPTVQCADWACQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
- C07C211/21—Monoamines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/01—Aerosol hair preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/02—Resin hair settings
Definitions
- the present invention relates generally to an alkyl allyl amine, more particularly to a polymer formed from an alkyl allyl amine, and even more particularly the present invention relates to a hair fixative composition utilized in styling gels, mousses or sprays (aerosol or pump) which includes a polymerizate of an alkyl allyl amine.
- the aqueous hair styling composition of the present invention contain a low concentration of volatile organic compounds (VOCs), with it being preferable that the VOCs make up 80% or less of the overall concentration of the hair spray formulation, and even more preferably that the VOCs make up 55% or less of the overall concentration of the hair spray formulation.
- VOCs volatile organic compounds
- Hair fixing or styling formulations are used to hold hair in a particular shape or configuration. They can take the form of, for example, hair sprays (aerosol or pump), styling gels, spray-on gels, or mousses. Hair styling formulations normally form a thin film of hair fixative resin when applied to the hair. This thin film of resin holds adjacent hairs together to retain a particular shape or configuration.
- a propellant i.e. an aerosol
- Hair fixing or styling formulations typically contain one or more volatile organic compound (VOC).
- VOCs as defined by the Environmental Protection Agency (EPA) contain at least one carbon atom and are typically used as solvents or propellants in the hair styling compositions. VOCs contribute to ground level air pollution in the presence of sunlight and air, and are volatile under ambient conditions.
- VOCs include, for example, Ci to Cj.2 straight or branched chain alcohols such as methanol, ethanol, propanol, isopropanol, or butanol; Ci to C 12 straight or branched chain hydrocarbons such as methane, ethane, propane, isopropane, isobutane, pentane, isopentane, or butane; or ethers such as dimethyl ether, or dimethoxymethane.
- Ci to Cj.2 straight or branched chain alcohols such as methanol, ethanol, propanol, isopropanol, or butanol
- Ci to C 12 straight or branched chain hydrocarbons such as methane, ethane, propane, isopropane, isobutane, pentane, isopentane, or butane
- ethers such as dimethyl ether, or dimethoxymethane.
- Aerosol hair sprays traditionally were formulated to contain
- the 55% VOC limit is much more of a challenge from a technical perspective than the 80% limit because the addition of large amounts of water to the hair spray formulation negatively affects both the hold performance and spray characteristics of the hair spray.
- Water impacts hold performance because it contributes to an increase in solution viscosity and surface tension. This results in increased initial curl droop and extends both tack time and dry time.
- Spray performance is impacted because an increase in viscosity (generally greater than 15 centipoise) of the spray solution leads to coarser, wetter sprays which are inefficient in coating the hair.
- the introduction of water causes compatibility problems in the ethanol/hydrocarbon solvent/propellant systems used for hair sprays, and can also lead to corrosion problems in steel cans used as vessels for the hair sprays.
- Water can also cause the composition, when sprayed, to form droplets or beads on the hair. These beads leave undesirable visible residue on the hair when dried, and can impart a raspy feel to the hair when combed.
- Water soluble hair fixative resins when used in low VOC hair styling formulations, are also more likely to become tacky after being applied to the hair.
- the water soluble hair fixative resins in a low VOC hair styling formulations may also have poor curl retention properties due to their inability to dry completely when applied to the hair.
- hair styling formulators have begun to redesign their hair styling compositions in order to formulate hair styling compositions or hair sprays which achieve low VOC levels, but yet which are acceptable for their intended use.
- hair style formulators have focussed on using solvents which are not classified as VOCs and on developing resins which are suitable in low VOC formulations.
- a resin is considered suitable when it can be applied to the hair in a carrier at low VOC and form a smooth feeling film and is resistant to cracking or breaking when combed.
- An example of a low VOC hair styling formulation already developed is U.S. Patent No. 5,176,898 to Goldberg, et al., which discloses an aqueous hair spray formulation having less than
- the aqueous hair spray formulation contains from 1 to 10 weight percent volatile silicone, preferably cyclomethicone or dimethicone copolyol, from 15 to 40 weight percent water/alcohol solution, from 5 to 60 weight percent propellant, from 1 to 10 weight percent water soluble hair fixative resin, and from 0.05 to 3.0 weight percent neutralizer/plasticizer.
- the present invention is directed to an alkyl allyl monomer and polymers thereof, particularly an alkyl allyl monomers useful in a hairspray formulation. More particularly the present invention is directed to a hair spray formulation which satisfies low VOC standards now in place and those anticipated in the future, and which overcomes a number of undesirable characteristics found in known low VOC hair spray formulations (i.e., decreased hold, increased tackiness, larger particle size, poor spray patterns, increased drying times, instability due to hydrolysis, increased can corrosion and poor compatibility with the solvent.
- the present invention is directed to an alkyl allyl amine represented by the formula:
- R ⁇ represents hydrogen or an allyl
- R 2 represents hydrogen or methyl
- n is an integer from 0 to 6
- R , R5 and Re each independently represent a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, a cycloalkylene (i.e. an aryl group) having 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
- R , R5 or Re represent a substituent other than hydrogen
- the alkyl portion of the alkyl allyl amine represented in formula (2) below be a branched alkyl group, more preferably, a tertiary alkyl group, more preferably a tertiary butyl group, and most preferably a tertiary octyl group:
- the alkyl group may also include methylene spacers (n>l) before the alkyl group begins to branch.
- the alkyl group may also include a hetero atom or a functional group. It is preferable that the alkyl allyl amine be a tertiary octyl mono allyl amine represented by formula (3) below:
- R2 represents hydrogen or methyl
- Ri of Formula (1) represent an allyl group, with R2 and R3 each independently representing a hydrogen or methyl group, with it being most preferred that R 2 and R3 be the same, and even more preferred that both R 2 and R3 both be hydrogen.
- Formula (4) below illustrates a preferred alkyl diallyl amine which has a substantial degree of "symmetry":
- R2 and R3 each independently represent hydrogen or methyl
- n is an integer from 0 to 6
- R , R5 and Re each independently represent a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having from 3 to 22 carbon atoms, a cycloalkylene (i.e. an aryl group) having from 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
- the alkyl portion of the diallyl amine be a branched alkyl group, more preferably a tertiary group (see Formula (2)) such as a tertiary butyl group, and even more preferred that it be a tertiary octyl group.
- a tertiary group such as a tertiary butyl group
- TODA t-octyl diallyl amine
- the present invention also relates to a hair fixative resin comprised of a polymer formed from an alkyl allyl amine monomer.
- the alkyl allyl amine monomer may be either a alkyl diallyl amine (i.e. formula (4)) or an alkyl mono allyl amine (i.e. formula (1) wherein Ri is hydrogen).
- the polymer may be generally represented by the formula:
- L, M, and Z may be random or repeating sequences of a conversion unit of a monomer with at least one of L, M and N being a conversion unit of an alkyl mono allyl amine (i.e. the polymerizate of formula (1) wherein Ri is H) or a conversion unit of alkyl diallyl amine of formula (7) shown below:
- R2 and R3 each independently represent hydrogen or methyl
- i 0 or 1 if ⁇ is 0, m is 1, and if t is 1, m is 0,
- n 0 to 6
- R , R5 and Re each independently represent hydrogen, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having from 3 to 22 carbon atoms, a cycloalkene (i.e. an aryl group) having from 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
- the polymer be formed as a homopolymer, that is, where L, M and N are all the conversion product of either the alkyl allyl amine monomer of formula (3), the conversion product of the alkyl diallyl amine of formula (5) (i.e. that of formula (7)), or a conversion unit of another known monomer. In the where L, M and N are different, the conversion units appear in a regular sequence. Even more preferably the polymer is a copolymer formed from, for example a monomer of Formula (5) and Formula (3), a methyl methacrylate monomer, or acrylic acid monomer or a combination thereof.
- L, M and N of formula (6) may be a conversion unit of any (meth)acrylate or (meth)acrylic acid (i.e., methyl methacrylate, acrylic acid) as well as an alkyl diallyl amine or alkyl mono allyl amine in a regular or random sequence.
- Other monomers which may be used in conjunction with either the alkyl diallyl amine and/or alkyl mono allyl amine of the present invention include a monomer selected from the group consisting of
- (meth)acrylates acrylamides, and (di)allyl ammonium salts.
- acrylamide, butyl aminoethyl methacrylate, methyl octyl diallyl ammonium bromide, dimethylamino ethylacrylate, tertiary-octyl acrylamide, and isobornyl methacrylate are suitable monomers useful in the present invention.
- the polymer of formula (6) include a conversion unit of the alkyl diallyl amine and that the alkyl group of the alkyl allyl amine be a branched alkyl group, more preferably a tertiary butyl group, and most preferably a tertiary octyl group.
- the polymer formed from a tertiary octyl diallyl amine monomer may be represented by formula (8) below:
- each of R2, R3, R4, R5, Re, t, m, n, L, N, x, y and z have the same definition as with regard to formula (6) and (7) above and wherein at least one of R , R5 and Re of formula (8) are an alkyl group, even more preferably a t-alkyl group represented by Formula (2) above.
- the polymer is incorporated in a hair spray or fixative formulation comprised of a volatile organic compound at a weight percentage of less than 80%, more preferably a hair spray formulation having a VOC concentration less than 55%.
- the hair spray formulation includes water and/pr other exempt solvents.
- the hair spray formulation preferably includes a VOC selected from the group consisting of methanol, an alcohol (i.e., ethanol, propanol, isopropanol, butanol) dimethoxymethane, and dimethyl ether.
- the hair spray formulation may also include acetone, typically classified as a solvent exempt from the
- the hair fixative formulation be formed at least in part with the monomer of formula (1), more preferably from a monomer wherein Ri of formula (1) is an allyl group and the alkyl portion of formula (1) is tertiary alkyl, more preferably t-octyl as shown in formula (4) above.
- the present invention is also directed to a method of manufacturing a hair fixative comprised of polymerizing an alkyl allyl monomer either as a homopolymer or a copolymer preferably along with methyl methacrylate and/or acrylic acid monomer. It is preferable that water and carrier solvents, including VOC solvents are mixed with the polymer and that, the overall concentration of VOCs in the hair spray formulation are less than 80% (wt/wt %) and more preferably less than 55% (wt/wt %) or less VOC.
- Figure 1 illustrates curl retention of TODA-based resins
- Example #1 - 40/20/40 TODA/AA/MMA in a low VOC hair spray formulations when compared to industry standards Amphoner LV71 and Eastman AQ48;
- Figure 2 illustrates curl retention of TODA-based resins (Sample #2 - 30/40/30 TODA/AA/MMA) in a low VOC hair spray formulation when compared to industry standards Amphomer LV71 and Eastman AQ48;
- Figure 3 illustrates the effect of VOC level (% Ethanol) on curl retention by 40/20/40 TODA/AA/MMA (Sample #1); and Figure 4 illustrates the effect of VOC level (% Ethanol) curl retention by 30/40/30 TODA/AA/MMA (Sample #2).
- the present invention is directed to a series of alkyl allyl amines useful as polymerizates in low VOC hair styling formulations.
- the alkyl allyl amines are prepared in accordance with the following formula:
- R? is equivalent to R 2 and/or R3 as defined elsewhere herein and represents hydrogen or methyl
- n is an integer from 0 to 6
- Re represents a suitable leaving group, preferably a halide, more preferably a halide selected from the group consisting of chloride and bromide, most preferably bromide
- R , R5 and R ⁇ each independently represent a hydrogen atom or an alkyl group having from 1 to 22 carbon atoms and wherein R 4 , R5, and Re may also represent a cycloalkyl group having from 3 to 22 carbon atoms, a cycloalkylene (i.e. an aryl group) having from 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
- R , R5 and Re do not represent hydrogen at the same time.
- the alkyl portion of the alkyl allyl amine be branched and more preferably a tertiary alkyl group.
- the ratios of alkyl mono allyl amine to alkyl diallyl amine synthesized and to some degree the amount of byproduct may be controlled by varying experimental conditions such as mole concentration of reaction substrates (i.e. allyl chloride) to the alkyl amine.
- reaction substrates i.e. allyl chloride
- the allyl halide be in the range of about 1.5 to about 2.5 times the mole concentration of alkyl amine, and more preferably about 2 times the mole concentration of the alkyl amine.
- the term "about” means plus or minus ten percent (10%) of the number at issue (i.e., "about 10" means in the range of 9-11). It has also been found that it is preferential to use allyl chloride when forming the mono allyl amine product and allyl bromide (both allyl chloride and allyl bromide are available from the Aldrich Chemical Company of St. Louis; MO) when forming the diallyl amine product. A typical synthesis of mono-allyl amine occurs as follows.
- t-octylamine (1,1,3,3 tetramethyl butyl amine) available from Aldrich is added at a mole concentration of 0.95 mole (129.25 g available at 95% purity) and 2.3 mole of 50% NaOH (184.0 g).
- allyl chloride at a mole concentration of 2-5 mole (197.3 g) over one hour at 25°C. The flask is observed for exothermic reaction and at the end of one hour heated to 55°C and stirred for 40 hours.
- the resulting product is about 69% t-octyl mono allyl amine, about 30% t-octyl amine and about 10% t-octyl diallyl amine.
- the reaction product is rotovapped resulting in a final reaction product of about 71% t-octyl mono- allyl amine, 27% t-octylamine, and 1.5% by-product. This product is then purified using flash liquid chromatography.
- alkyl diallyl amine of the present invention .95 moles of t-octyl amine, 2.3 moles of NaOH (50%) and an excess of allyl chloride (2.5 moles) are mixed in a reaction flask.
- the reaction flask is kept at 15 psi and 85°C while stirring for 8 hours.
- the temperature is then increased to 100°C for an additional 8 hours. This results in about 10% t-octyl diallyl amine, about 82% t-octyl mono allyl amine, and about 8% t-octyl amine.
- the pressure is adjusted to 1 atm and 1 mole of allyl bromide is added to a 2 liter reaction vessel which is then heated at 85°C for an additional 12 hours.
- the resulting reaction product is comprised of about 88% t-octyl diallyl amine, about 2.2% mono allyl amine and about 8.8% by-product.
- the t-octyl diallyl amine is then purified via flash chromatography.
- alkyl mono allyl amines and alkyl diallyl amines are synthesized and tested for their suitability in low VOC hair spray formulations. These include the following alkyl ally amines:
- alkyl amines From these alkyl amines it was determined that the most suitable formulations were those having branch alkyl groups, and more preferably those classified as alkyl diallyl amines, even more preferably, branched alkyl diallyl amines, and most preferably tertiary alkyl diallyl amines.
- acrylic acid AA
- AM acrylamide
- MMA methyl methacrylate
- BAEMA butyl aminoethyl methacrylate
- MODAAB methyl octyl diallyl ammonium bromide
- DAEA dimethylamine ethylacrylate
- TOAM tertiary-octyl acrylamide
- the hair was arranged so that it was evenly distributed across a one-inch area within the center of the piece of wood.
- a second layer of hot glue was placed over the hair in contact with the wood.
- a second identical piece of wood was placed over the glue so that the root end of the hair was securely sandwiched between the two pieces of tongue depressor.
- the glue was allowed to dry a few minutes and the root ends of the hair was trimmed so that it was flush with the wood.
- the hair tress prepared as above was immersed in 15% Triton X-100 (octylphenoxy polyethoxyethanol nonionic surfactant, raw material code OM-JJ21-00) solution for 2 minutes to wash it.
- the hair tress was rinsed for 2 minutes under running de-ionized water.
- the hair tress was immersed and then rinsed in 1% (by weight) aqueous sodium chloride solution (1 hour immersion for 2 minutes) and then rinsed with de-ionized water.
- the de-ionized water was changed and the hair tress was soaked in fresh de-ionized water for 3 hours.
- the de-ionized water was changed again and the hair tress was again soaked in fresh deionized water overnight.
- the hair tress was then removed from the water and allowed to air dry for 24 hours. Once dry, the clean hair tress was placed in a plastic bag and stored flat for future use.
- the clean curl retention tree was secured by a stainless steel curl retention clamp and the ends are trimmed to 6" length using a sharp paper cutter.
- the trimmed hair was detangled utilizing the wide end of a comb and then combed with the fine end of the comb twice.
- the tress was immersed in 100 mL of hair setting solution for 10 seconds. Any excess solution was removed by running the hair tress between the fingers twice.
- the hair was then detangled and combed twice with the fine end of the comb. Starting with the hair at the left edge of the roller, the hair was wound onto the roller ending its wind on the right-hand edge of the roller. The curled hair was secured with a clip.
- the rolled tresses were hung on the curl retention board (a peg board marked with gradations for measuring the length of the curl) and conditioned at 50% relative humidity overnight. The next day about 600 mL de-ionized water was added to each of two glass dishes in a humidity chamber. Sodium sulfite was poured into each dish to cover the bottom, making a saturated solution that allowed the chamber to achieve 95% relative humidity. Once the chamber reached 95% relative humidity, each clamp was pulled to the front of the peg to keep the tress from touching the board. Or is to be noted that at this point, the curl retention board with the tresses was still outside of the humidity chamber.
- Each of the tresses are unwound are at a time into a helical configuration, and the initial length (Lo) is recorded.
- the rack of curls was placed into the humidity chamber and a timer was set for 15 minutes.
- the length of each curl (hi) was measured.
- Subsequent timings were studied at the beginning of recording the length of the first tress.
- the temperature and relative humidity at each interval was to calculate % Curl Retention (% CR) equation 1 was used:
- the unsaturated polymerizable monomers were combined by a technique known as addition in which free radicals are the initiating agents that react with the double bond of the monomer by adding to it on one side and at the same time producing a new free electron on the other. By this mechanism the chain becomes self-propagating. Polymerization as described here may also occur by condensation involving the splitting out of water molecules by two reacting monomers and by so-called oxidative coupling.
- the polymerization techniques described herein can be: (1) in the gas phase at high pressures and temperatures (200°C); (2) in solution at normal pressure and temperatures from -70° to +70°C; (3) bulk or batch polymerization at normal pressure at 150°C; (4) in suspension at normal pressure at 60° to 80°C; and (5) in emulsion form at normal pressure at - 20° to + 60°C (used for copolymers).
- catalysts of the peroxide type sometimes are necessary with these methods.
- hair spray formulation samples were prepared with varying levels or ratios of tertiary-octyl diallyl amine monomer
- TODA methyl methacrylate
- MMA methyl methacrylate
- AA acrylic acid
- 30/40/30 TODA/AA MMA is applicable for hair setting applications, and would be preferred over 40/20/40 TODA/AA/MMA.
- 40/20/40 TODA/AA/MMA (Sample #1) may be more suitable if an exempt VOC solvent such as acetone is utilized.
- VOC solvent such as acetone
- the aerosol concentrate is the base formulation for a 55% VOC aerosol spray while generally results in 5% resin solids when charged with propellant at 65% concentrate and 35% propellant.
- the final aerosol formula would contain approximately: 5% resin solids, 20% ethanol, 40% de-ionized water and 35% propellant.
- the propellant used in this study was dimethyl ether (DME), which is more compatible with water than hydrocarbons such as isobutane and propane. DME, however, is also classified as a VOC, thus, the 35% DME plus the 20% ethanol combine to account for 55% VOC in this aerosol formula. Aerosol formulations were prepared by weighing the concentrate into a shielded aerosol reaction vessel, sealing with a SeaquistPerfect valve and charging with the required weight of dimethyl ether.
- DME dimethyl ether
- Brookfield viscosity was measured at 25 ⁇ 1°C on a Brookfield
- Viscometer Model DVLV-III equipped with a UL adapter and spindle. Resin samples were evaluated for curl retention at 5% solids according to the method described above. To test film clarity, film was drawn from 55% and 80% VOC solutions on a 25 x 75 mm plain glass microscope slide, allowed to dry and visually evaluated for clarity.
- Sample #1 40/20/40 TODA/AA/MMA, was soluble at 5% solids in 55% and 80% VOC solutions but somewhat insoluble in the aerosol concentrate at 8% solids and 30% ethanol. Solubility at 55% and 80% VOC was also achieved with Sample #2, the 30/40/30 TODA/AA/MMA composition. This sample was also partially soluble in the aerosol concentrate; however, neutralization with AMP-95 (2-amino-2- methyl-1-propanol), 95% solution (Angus Chemical) was preferred in all the formulations to better solubilize the samples.
- the aerosol concentrate is described as only partially soluble because after several hours of stirring there remained a small amount of insoluble material remaining. Since there was such a small amount of this insoluble material, it was filtered off and the remaining supernatant was used to prepare a 55% VOC aerosol formulation with dimethyl ether. This solution remained clear; however, there was evidence of some incompatibility in areas of localized propellant concentration as it was charged to the vessel.
- a viscosity range of about 15-17 centipoise is an acceptable range, but for aerosol formulations, in particular, 3-4 cps to achieve the preferred spray characteristics in 55% VOC hair spray formulation.
- the data shows that while both samples achieve acceptable target viscosity range, Sample 1 achieves the preferred target viscosity range for aerosols and thus is preferable over Sample 2.
- the molecular weight of Sample 2 was targeted to be higher than that of Sample 1 which probably contributed to the higher viscosity.
- the viscosity of Eastman AQ 48 was in the optimal range of 3-4 at 55% VOC. This would be as expected since the resin was commercialized to meet the 55% VOC requirements.
- Amphomer LV 71 has a viscosity higher than that of Eastman AQ 48 at 55% VOC; however, Amphomer is advocated primarily for
- Table 3 also highlights the clarity of films formed by 55% and 80% VOC formulations of the four resins.
- Sample #1 formed cloudy films at both 55% and 80% VOC.
- Sample #2 film clarity was achieved at both 55% and 80% VOC.
- Amphomer LV 71 formed a clear film at 80% VOC, however, at 55% VOC the film was slightly cloudy.
- Eastman AQ 48 formed a clear film at 55% VOC.
- Curl retention results are summarized in Table 4. Each chemistry sample was evaluated at 55% and 80% VOC in separate test series against 55% VOC formulas of Amphomer LV 71 and Eastman AQ 48 and 80% VOC Amphomer LV 71. Actual curl retention versus time curves are shown in Figures 1 and 2 for the respective samples. The data from these curves, as well as the final results in Table 4, show that while 40/20/40 TODA/AA/MMA, Sample #1, was not as ideal for curl retention, achieving only 56% and 34% retention at 55% and 80% VOC, respectively, adjusting the composition to 30/40/30 TODA/AA/MMA, Sample #2, improves retention performance to 93% at 55% VOC and 76% VOC at 80% VOC.
- FIG. 3 The performance of 30/40/30 TODA/AA/MMA matches those of both Amphomer LV 71 and Eastman AQ 48 at 55% VOC.
- Figures 1 and 2 show the effects of VOC level on curl retention by the resins.
- Figure 4 and Figure 4 the effect of VOC level on curl retention by 40/20/40 TODA/AA/MMA (Fig. 3) and 30/40/30 TODA/AA/MMA (Fig. 4) respectively.
- Figure 4 illustrates just how closely the 30/40/30 TODA/AA/MMA parallels the performance of Amphomer LV 71 at varying VOC levels. The decrease in curl retention with increasing ethanol concentration has been noted in previous studies.
- the second sample showed a clear improvement in the target attributes. With neutralization, it was soluble in 55% and 80% ethanol solutions and mostly soluble in the aerosol concentrate and aerosol formulation. It formed a clear film on glass and performed as well as commercially available hair setting resins in curl retention testing.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU53178/99A AU5317899A (en) | 1998-07-22 | 1999-07-19 | Alkyl allyl amines and low voc hair styling compositions using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/120,699 | 1998-07-22 | ||
US09/120,699 US6361801B1 (en) | 1998-07-22 | 1998-07-22 | Alkyl allyl amines and low voc hair styling compositions using same |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000005192A2 true WO2000005192A2 (en) | 2000-02-03 |
WO2000005192A3 WO2000005192A3 (en) | 2000-05-11 |
Family
ID=22392010
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/016301 WO2000005192A2 (en) | 1998-07-22 | 1999-07-19 | Alkyl allyl amines and low voc hair styling compositions using same |
Country Status (3)
Country | Link |
---|---|
US (1) | US6361801B1 (en) |
AU (1) | AU5317899A (en) |
WO (1) | WO2000005192A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2821032A1 (en) | 2001-02-21 | 2002-08-23 | Jacques Oury | Refrigerated installation to transport perishable products or medical products at a required constant low temperature to ensure that they do not deteriorate |
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DE4234743A1 (en) * | 1992-10-15 | 1994-04-21 | Wella Ag | Means for setting the hair |
EP0791351A1 (en) * | 1996-02-20 | 1997-08-27 | L'oreal | Composition containing a fixative polymer, an n-C5-C8-alkane and acetone |
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GB1216399A (en) | 1967-12-15 | 1970-12-23 | Calgon Corp | Copolymers of diallyl ammonium compounds |
FR2390950A1 (en) | 1977-05-17 | 1978-12-15 | Oreal | NEW COSMETIC COMPOSITIONS FOR HAIR AND SKIN BASED ON COPOLYMERS CARRYING TERTIARY AMINE AND / OR QUATERNARY AMMONIUM FUNCTIONS |
DE3528548A1 (en) | 1985-08-08 | 1987-02-19 | Dow Chemical Gmbh | PRODUCTION OF AN ALLYLAMINE AND QUATERNAIL DIALLYLAMMONIUM COMPOUNDS THEREOF |
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-
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---|---|---|---|---|
FR2821032A1 (en) | 2001-02-21 | 2002-08-23 | Jacques Oury | Refrigerated installation to transport perishable products or medical products at a required constant low temperature to ensure that they do not deteriorate |
Also Published As
Publication number | Publication date |
---|---|
AU5317899A (en) | 2000-02-14 |
WO2000005192A3 (en) | 2000-05-11 |
US6361801B1 (en) | 2002-03-26 |
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